Polyarylene polymers and processes for preparing

ABSTRACT

Provided are sulfone-containing polyarylene polymers. Also provided are monomers and processes for preparing the polymers. The polyarylene polymers are suitable for use as engineering polymers.

FIELD OF THE INVENTION

The present invention is directed to polyarylene polymers useful asengineering polymers, and to processes and monomers for use in preparingthe polymers.

BACKGROUND

High performance polymers (HPP) are a fast growing portion of theengineering polymers market. These polymers offer excellent performanceunder harsh operating conditions by virtue of their high temperaturestability, chemical resistance, high tensile properties, and abrasionresistance. However, existing polymers all display compromises incertain attributes while excelling in others. In general, thermoplasticHPP are either semi-crystalline or amorphous with the former typicallyoffering superior chemical and abrasion resistance and the lattersuperior thermal resistance and mechanical toughness. The most commonsemi-crystalline HPP are polyphenylene sulfide, liquid-crystalpolyesters, and polyether ketones, and the most common amorphous HPP arepolyether sulfones and thermoplastic polyimides. These polymers aretypically filled with glass fiber, carbon fiber, graphite, and othermaterials as reinforcements to improve their tensile properties,dimensional stability, and wear resistance.

One particularly new type of HPP is self-reinforced polyphenylene (SRP),an amorphous polymer with many of the attributes of the semi-crystallinepolymers. SRP offers a unique combination of tensile properties,abrasion resistance, chemical resistance, and thermal stability. The keyto its high performance is the rigid-rod phenylene backbone which makesfurther fiber reinforcement unnecessary. The polyphenylene backbone canbe substituted with phenylketone groups to render it amorphous and allowfor thermal processing. For example, Wang and Quirk, Macromolecules,1995, 28 (10), p. 3495, disclose that poly(2,5-benzophenone) is thoughtto be amorphous due to the head-tail disorder introduced in the polymerbackbone during polymerization of 2,5-dichlorobenzophenone and that thedegree of disorder has an effect on the glass transition temperature(Tg) of the polymer.

Since the ketone version of SRP is already amorphous, but retains manyattributes of a semi-crystalline HPP, a sulfone version of SRP, such aspoly(2,5-diphenylsulfone) (PDS), has the potential to expand its set ofproperties without compromising those normally due to semi-crystallinityand expand its utility into applications currently meet only by highperformance polyimide products. However, the polymerization conditionsthat are successful for poly(2,5-benzophenone) do not produce highmolecular weight PDS.

SUMMARY OF THE INVENTION

One aspect of the present invention is a polymer comprising repeatingunits of Formula (I):

wherein T is a bulky aromatic group.

DETAILED DESCRIPTION

Disclosed is a polymer comprising repeating units of Formula (I):

wherein T is a bulky aromatic group. The repeat unit can be referred toas a rigid-rod polyarylene; however it has a higher degree of structuralorder than typical rigid-rod polyphenylenes by virtue of itssymmetrically meta-disubstituted biphenylene structure.

By bulky aromatic group is meant an aromatic carbocyclic group having asingle ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiplecondensed rings in which at least one is aromatic, (e.g.,1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl). Thebulky aromatic group can be optionally substituted with a non-reactivegroup, such as alkyl, other aromatic groups, and other non-reactivefunctional groups such as ethers. In one embodiment, T is phenyl.

The term “polymer” is intended to include homopolymers, copolymers, andterpolymers.

The polymer can have a number average molecular weight (M_(n)) of atleast about 5,000, or at least about 15,000, or at least about 19,000.The polymer can also have a weight average molecular weight (M_(w)) ofat least 80,000, or at least 200,000.

In one embodiment, the polymer is a homopolymer. In another embodiment,the polymer is a copolymer, containing other repeat units. Such otherrepeat units can maintain the rigid-rod nature of the biphenylenebackbone of the polymer comprising repeating units of Formula (I), orcan introduce varying degrees of flexibility. Appropriate rigid-rodrepeat units can be similar in chemical composition and structure topreserve the physical properties of the polymer comprising repeatingunits of Formula (I) or can be different to introduce additionalproperties required for processing and/or for the desired application ofthe polymer. In one embodiment, the polymer can additionally compriserepeating units of Formula (II):

where T′ is a bulky aromatic group. In one embodiment, T′ is phenyl.These embodiments introduce sufficient head-tail disorder in thephenylene repeat units of the polymer to modify its physical propertieswhile preserving the rigid-rod structure. Polymers comprising repeatingunits of both Formula (I) and Formula (II) can have a number averagemolecular weight (M_(n)) of at least about 5,000, or at least about9,000, or at least about 60,000. The polymers can also have a weightaverage molecular weight (M_(w)) of at least 40,000, or at least300,000.

A suitable monomer to prepare polymers comprising repeating units ofFormula (I) is a compound of Formula (IA):

wherein T is as described above and X is independently Br or Cl,typically Cl, and has a higher degree of structural order than typicalrigid-rod polyphenylenes by virtue of its symmetricallymeta-disubstituted biphenylene structure.

A suitable monomer to prepare polymers comprising repeating units ofFormula (II) is a compound of Formula (IIA):

wherein T′ is as described above and X′ is independently Br or Cl,typically Cl. Although the sulfone group is ortho-substituted withrespect to one of the halide groups, high molecular weight is attainableduring copolymerization with meta-substituted monomer of Formula (IA).

The polymer comprising repeating units of Formula (I) with repeatingunits of Formula (II) can be block, random, or alternating copolymers.

The monomers of Formulae (IA) and (IIA) may be reacted to form largermonomeric units that are then polymerized alone or with other monomersto form the polymers disclosed herein. For example, a copolymer(-A-)_(x)(—B—)_(y) may be formed by copolymerizing monomer X-A-X withmonomer X—B—X, or by forming larger monomer X-A-B—X and polymerizingthat monomer. In both cases, the resulting polymer is considered acopolymer derived from monomer X-A-X and monomer X—B—X.

The monomers of Formula (IA) and (IIA), and the reactants used toprepare the monomers, may be obtained commercially or be prepared usingany known method in the art or those disclosed herein.

The practical upper limit to the number of monomeric units in thepolymer is determined in part by the desired solubility of a polymer ina particular solvent or class of solvents. As the total number ofmonomeric units increases, the molecular weight of the polymerincreases. The increase in molecular weight is generally expected toresult in a reduced solubility of the polymer in a particular solvent.Moreover, in one embodiment, the number of monomeric units at which apolymer becomes substantially insoluble in a given solvent is dependentin part upon the structure of the monomer. For example, a polymercomposed of disubstituted biphenylene-based monomers may becomesubstantially insoluble in an organic solvent if the resulting polymerbecomes too rigid in the course of polymerization and the biphenylenerepeat unit is too structurally regular due to the structure of T. Inanother embodiment, the number of monomeric units at which a copolymerbecomes substantially insoluble in a given solvent is dependent in partupon the ratio of the comonomers. As another example, a copolymercomposed of several rigid monomers may become substantially insoluble inan organic solvent when ratio of disubstituted biphenylene monomericunits to substituted phenylene monomeric units is too large. Theselection of polymer molecular weight, polymer and copolymercomposition, and a solvent is within the purview of one skilled in theart.

The polymerizations as described herein can generally be performed bysynthetic routes in which the leaving groups of the monomers areeliminated in carbon-carbon bond-forming reactions. Such carbon-carbonbond-forming reactions are typically mediated by a zerovalent transitionmetal complex that contains neutral ligands. In one embodiment, thezerovalent transition metal complex contains nickel or palladium. By“complex”, as used herein, is meant one or more metal cations togetherwith associated anions and/or neutral ligands.

Neutral ligands are defined as ligands that are neutral, with respect tocharge, when formally removed from the metal in their closed shellelectronic state. Neutral ligands contain at least one lone pair ofelectrons, a pi-bond, or a sigma bond that is capable of binding to thetransition metal. For the processes described herein, the neutral ligandmay also be a combination of two or more neutral ligands. Neutralligands may also be polydentate when more than one neutral ligand isconnected via a bond or a hydrocarbyl, substituted hydrocarbyl or afunctional group tether. A neutral ligand may be a substituent ofanother metal complex, either the same or different, such that multiplecomplexes are bound together. Neutral ligands can include carbonyls,thiocarbonyls, carbenes, carbynes, allyls, alkenes, olefins, cyanides,nitriles, carbon monoxide, phosphorus containing compounds such asphosphides, phosphines, or phosphites, acetonitrile, tetrahydrofuran,tertiary amines (including heterocyclic amines), ethers, esters,phosphates, phosphine oxides, and amine oxides.

Three synthetic methods based on zerovalent transition metal compoundsthat can be used to prepare the polymers are described herein. In eachmethod, the zerovalent transition metal compound that is the activespecies in carbon-carbon bond formation can be introduced directly intothe reaction, or can be generated in situ under the reaction conditionsfrom a precursor transition metal compound and one or more neutralligands.

In a first synthetic method, disclosed in Yamamoto, Progress in PolymerScience, Vol. 17, p 1153 (1992), the dihalo derivatives of the monomersare reacted with stoichiometric amounts of a zerovalent nickel compound,such as a coordination compound like bis(1,5-cyclooctadiene)nickel(0),and a neutral ligand, such as triphenylphosphine or 2,2′-bipyridine.These components react to generate the zerovalent nickel compound thatis the active species in the polymerization reaction. A second neutralligand, such as 1,5-cyclooctadiene, can be used to stabilize the activezerovalent nickel compound.

In a second synthetic method, disclosed in U.S. Pat. No. 5,962,631,loyda et al., Bulletin of the Chemical Society of Japan, Vol. 63, p. 80(1990), and Colon et al., Journal of Polymer Science, Part A, PolymerChemistry Edition, Vol. 28, p. 367 (1990), the dihalo derivatives of themonomers are reacted with catalytic amounts of a divalent nickelcompound in the presence of one or more neutral ligands in the presenceof stoichiometric amounts of a material capable of reducing the divalentnickel ion to zerovalent nickel.

The catalyst is formed from a divalent nickel salt. The nickel salt canbe any nickel salt that can be converted to the zerovalent state underreaction conditions. Suitable nickel salts are the nickel halides,typically nickel dichloride or nickel dibromide, or coordinationcompounds, typically bis(triphenylphosphine)nickel dichloride or(2,2′-bipyridine)nickel dichloride. The divalent nickel salt istypically present in an amount of about 0.01 mole percent or greater,more typically about 0.1 mole percent or greater or 1.0 mole percent orgreater. The amount of divalent nickel salt present is typically about30 mole percent or less, more typically about 15 mole percent or lessbased on the amount of monomers present.

The polymerization is performed in the presence of a material capable ofreducing the divalent nickel ion to the zerovalent state. Suitablematerial includes any metal that is more easily oxidized than nickel.Suitable metals include zinc, magnesium, calcium and lithium, with zincin the powder form being typical. At least stoichiometric amounts ofreducing agent based on the monomers are required to maintain the nickelspecies in the zerovalent state throughout the reaction. Typically,about 150 mole percent or greater, more typically about 200 mole percentor greater, or about 250 mole percent or greater is used. The reducingagent is typically present in an amount of about 500 mole percent orless, about 400 mole percent or less, or about 300 mole percent or lessbased on the amount of monomer.

Also present are one or more compounds capable of acting as a ligand.Suitable ligands are neutral ligands as described above, and includetrihydrocarbylphosphines. Typical ligands are monodentate, such astriaryl or trialkylphosphines like triphenylphosphine, or bidentate,such as 2,2′-bipyridine. A compound capable of acting as a monodentateligand is typically present in an amount of from about 10 mole percentor greater, or about 20 mole percent or greater based on the monomer. Acompound capable of acting as a monodentate ligand is typically presentin an amount of about 100 mole percent or less, about 50 mole percent orless, or about 40 mole percent or less. A compound capable of acting asa bidentate ligand is typically present in an amount that is about amolar equivalent or greater based on the divalent nickel salt.Alternatively, the bidentate ligand can be incorporated into the nickelsalt as a coordination compound as described above.

In a third synthetic method, disclosed in PCT application WO 00/53656and U.S. Pat. No. 6,353,072, a dihalo derivative of one monomer isreacted with a derivative of another monomer having two leaving groupsselected from boronic acid (—B(OH₂) or boronate salt, boronic acidesters (—BOR₂) or (—B(ORO)), and boranes (—BR₂), where R is generally ahydrocarbyl group, in the presence of a catalytic amount of a zerovalentpalladium compound containing a neutral ligand as described above, suchas tetrakis(triphenylphosphine)palladium(0). If the leaving group is aboronic ester or borane group, the reaction mixture should includesufficient water or an organic base to hydrolyze the boronic ester orborane group to the corresponding boronic acid group. The diboronicderivative of a monomer can be prepared from the dihalo derivative byknown methods, such as those described in Miyaura et al., SyntheticCommunication, Vol. 11, p. 513 (1981) and Wallow et al., AmericanChemical Society, Polymer Preprint, Vol. 34, (1), p. 1009 (1993).

All of the synthetic methods disclosed herein can be performed in thepresence of a compound capable of accelerating the reaction. Suitableaccelerators include alkali metal halides such as sodium bromide,potassium bromide, sodium iodide, tetraethylammonium iodide, andpotassium iodide. The accelerator is used in a sufficient amount toaccelerate the reaction, typically 10 mole percent to 100 mole percentbased on the monomer.

The reactions are typically run in a suitable solvent or mixture ofsolvents, that is a solvent that is not detrimental to catalyst,reactant and product, and preferably one in which the reactants andproducts are soluble. Suitable solvents include N,N-dimethylformamide(DMF), toluene, tetrahydrofuran (THF), acetone, anisole, acetonitrile,N,N-dimethylacetamide (DMAc), and N-methylpyrrolidinone (NMP). Theamount of solvent used in this process can vary over a wide range.Generally, it is desired to use as little solvent as possible. Thereactions are typically conducted in the absence of oxygen and moisture,as the presence of oxygen can be detrimental to the catalyst and thepresence of a significant amount of water could lead to prematuretermination of the process. More typically, the reaction is performedunder an inert atmosphere such as nitrogen or argon.

The reactions can be performed at any temperature at which the reactionproceeds at a reasonable rate and does not lead to degradation of theproduct or catalyst. Generally, the reaction is performed at atemperature of about 20° C. to about 200° C., more typically less than100° C. The reaction time is dependent upon the reaction temperature,the amount of catalyst and the concentration of the reactants, and isusually about 1 hour to about 100 hours.

The polymers prepared by the disclosed methods can be recoveredaccording to conventional techniques including filtration andprecipitation using a non-solvent. They also can be dissolved ordispersed in a suitable solvent for further processing.

The polymers disclosed herein are suitable for use as engineeringpolymers in applications such as, for example, molecular reinforcementin nanocomposites, mineral-filled and fiber-reinforced composites,injection and compression-molded parts, fibers, films, sheets, papers,and coatings, and can be processed both thermally as is typical forthermoplastic polymers and in solution after dissolving in suitablesolvents depending on the requirements of the application.

EXAMPLES Activation of Copper Powder

Copper powder was activated according to the procedure in Vogel'sTextbook of Practical Organic Chemistry, 4^(th) Edition, 1981, Longman(London), pages 285-286. Copper bronze (50 g, Aldrich Chemical Company,Milwaukee, Wis.) was stirred for 10-20 minutes with a solution of iodine(10 g) dissolved in acetone (500 mL) to give a gray mixture. The copperwas filtered off, washed acetone, and added to a solution ofhydrochloric acid (150 mL) and acetone (150 mL). The mixture was stirreduntil the gray solids dissolved then the copper was filtered off andwashed well with acetone. The activated copper solids were dried underhigh vacuum and transferred to a glove box for storage and handling.

2,5-Dibromobenzenesulfonic acid, sodium salt

A modification of the published procedures of H. Borns, Annalen derChemie 1877, 187, 350 was used. A 300 mL round-bottom flask equippedwith a reflux condenser, stirring bar, and gas inlet was charged with1,4-dibromobenzene (118 g, 0.50 moles) and 30% fuming sulfuric acid (76mL). The mixture was heated to 150° C. for 3 hours under nitrogen togive a clear solution. The solution was cooled to room temperature togive a solidified mass and transferred into a beaker with water to givea slurry. The slurry was treated with 50% sodium hydroxide solution (130g) and diluted to 900 mL with water with heating to disperse theprecipitated solids. The mixture was cooled to room temperature and thesolids collected by vacuum filtration under a rubber dam. The solidswere washed with two times with isopropanol (200 mL) and air dried onthe filter then dried under vacuum at 100° C. to give 159 g (93% crudeyield). The product was recrystallized from ethanol/water (4:1) anddried under vacuum at 150° C. to give 146 g (86% yield) of2,5-dibromobenzenesulfonic acid, sodium salt. ¹H NMR (DMSO-d₆): 7.42(dd, 8.4, 2.6 Hz, 1H), 7.53 (d, 8.4 Hz, 1H), 8.01 (d, 2.6 Hz, 1H).

4,4′-Dibromobiphenyl-2,2′-disulfonic acid, sodium salt

A modification of the published procedures of Courtot and Lin in Bull.Soc. Chim. Fr. 1931, 49, 1047 was used. Inside a glove box, a 500 mLround-bottom flask equipped with a reflux condenser, stirring bar, andgas inlet was charged with 2,5-dibromobenzenesulfonic acid, sodium salt(73 g, 0.216 moles), activated copper bronze (27 g, 0.43 moles), andDMAc (200 mL). The mixture was heated to 120° C. overnight undernitrogen. The mixture was poured into water (1 L) and the solid removedby vacuum filtration. The filtrate was evaporated and the residue driedat 100° C. under vacuum. The solids were recrystallized fromacetonitrile/water (10:1) after treating with decolorizing carbon anddried under vacuum at 60-150° C. to give 48.13 g (86% yield) of4,4′-dibromobiphenyl-2,2′-disulfonic acid, sodium salt. ¹H NMR(DMSO-d₆): 7.19 (d, 8.3 Hz, 2H), 7.42 (dd, 8.3 and 2.1 Hz, 2H), 7.96 (d,2.1 Hz, 2H).

4,4′-Dibromobiphenyl-2,2′-disulfonyl dichloride

A modification of the published procedures of Courtot and Lin in Bull.Soc. Chim. Fr. 1931, 49, 1047 was used. Inside a glove box, a 200 mLround-bottom flask equipped with a reflux condenser, stirring bar, andgas inlet was charged with 4,4′-dibromobiphenyl-2,2′-disulfonic acid,sodium salt (51.6 g, 0.100 moles), phosphorus pentachloride (46 g, 0.22moles), and phosphorus oxychloride (30 mL). The mixture was heated to amild reflux (152° C.) for 6 hours under nitrogen. The mixture was pouredonto ice (1 kg) and stirred until the solids were finely divided. Thesolids were collected by vacuum filtration, washed well with water, andair dried on the filter then dried under vacuum at 75° C. to give 50.7g. The solids were recrystallized from toluene after treating withdecolorizing carbon, collected by vacuum filtration, and dried undervacuum at 60° C. to give 42.59 g (84% yield) of4,4′-dibromobiphenyl-2,2′-disulfonyl dichloride. ¹H NMR (CDCl₃): 7.38(d, 8.2 Hz, 2H), 7.91 (dd, 8.2, 2.0 Hz, 2H), 8.37 (d, 2.0 Hz, 2H).

2,5-Dibromobenzenesulfonyl chloride

A modification of the published procedures of Moroni et al. inMacromolecules 1994, 27, 562 was used. A 300 mL round-bottom flaskequipped with a reflux condenser, stirring bar, and gas inlet wascharged with 1,4-dibromobenzene (50 g, 0.21 moles) and chlorosulfonicacid (100 mL). The mixture was heated to 90° C. for 2 hours undernitrogen to give a clear solution. The solution was cooled to roomtemperature and carefully poured onto ice (1 kg) to give a precipitate.The solids were collected by vacuum filtration, washed well with water,and air dried on the filter then dried under vacuum at 50° C. to give68.36 g. The product was recrystallized from cyclohexane after treatingwith decolorizing carbon, collected by vacuum filtration, and dried at50° C. under vacuum to give 55.37 g (79% yield) of2,5-dibromobenzenesulfonyl chloride. ¹H NMR (CDCl₃): 7.66 (dd, 8.4, 2.3Hz, 1H), 7.72 (d, 8.4 Hz, 1H), 8.30 (d, 2.3 Hz, 1H).

Example 1 2-Benzenesulfonyl-1,4-dibromobenzene

A 100 mL round-bottom flask equipped with a reflux condenser, stirringbar, and gas inlet was charged with 2,5-dibromobenzenesulfonyl chloride(10 g, 30 mmoles) and benzene (30 mL). Aluminum chloride (4 g, 30mmoles) was added and the mixture stirred until dissolved. The solutionwas heated to reflux for 2 hours. The solution was cooled to roomtemperature and poured onto 150 g ice mixed with 50 mL hydrochloricacid. The precipitated solids were collected by filtration and washedwith water. The filtrate was extracted with ether and the organicextracts were washed twice with water, dried with magnesium sulfate,filtered, and evaporated. The precipitated and extracted products werecombined to give 11.33 g of impure product. The solids wererecrystallized from ethanol after treating with decolorizing carbon togive 3.82 g (34% yield) of 2-benzenesulfonyl-1,4-dibromobenzene. ¹H NMR(DMSO-d₆): 7.65 (dd, 7.7, 7.4 Hz, 2H), 7.76 (t, 7.4 Hz, 1H), 7.76 (d,8.4 Hz, 1H), 7.85 (dd, 8.4, 2.4 Hz, 1H), 7.98 (d, 7.7 Hz, 2H), 8.40 (d,2.4 Hz, 1H).

This reaction was repeated on a larger scale (100 mmol) with 6 hours atreflux and worked up by extracting the hydrolyzed mixture withdichloromethane then drying with sodium carbonate. The impure productwas recrystallized from ethanol to give 13.7 g (36% yield). ¹³C NMR(CDCl3): 120.23 (C), 122.31 (C), 129.21 (2CH), 129.39 (2CH), 134.20(CH), 134.46 (CH), 137.38 (CH), 137.92 (CH), 139.69 (C), 142.04 (C). MS(M+H⁺): m/e 376.8654 (100%), 374.8680 (50%), 378.8630 (49%); exact massfor C₁₂H₉O₂Br₂S₁, 376.8670 (100%), 374.8690 (51.4%), 378.8649 (48.6).

Example 2 2,2′-Bis-benzenesulfonyl-4,4′-dibromobiphenyl

Inside a glove box, a 100 mL round-bottom flask equipped with a stirringbar, reflux condenser, and a septum was charged with2-benzenesulfonyl-1,4-dibromobenzene (7.52 g, 20 mmoles), activatedcopper powder (2.54 g), and DMAc (20 mL). The flask was heated to 120°C. under nitrogen for 2 hours. The mixture was cooled to roomtemperature, poured into acetone, and filtered using a 5 μm PTFEmembrane filter. The solvents were evaporated and the residue driedunder high vacuum to give 6.40 g solids. The mixture was purified bycolumn chromatography using silica gel and dichloromethane to give 1.74g (29% yield) of 2,2′-bis-benzenesulfonyl-4,4′-dibromobiphenyl. ¹H NMR(DMSO-d₆): 6.89 (d, 8.2 Hz, 2H), 7.54 (m, 4H), 7.55 (m, 4H), 7.69 (m,2H), 7.86 (dd, 8.2, 2.1 Hz, 2H), 8.22 (d, 2.1 Hz, 2H).

The reaction was repeated several times at 100-120° C. varying the timefrom 3-7 hours without a substantial change in the yield after columnchromatography. The combined products (9.46 g) were recrystallized twicefrom toluene to give 5.44 g pure compound. ¹³C NMR (DMSO-d₆): 122.30(2C—Br), 127.68 (4CH), 129.40 (4CH), 131.36 (2CH), 133.68 (2 CH), 133.93(2CH), 135.06 (2C), 135.38 (2CH), 140.25 (2C—SO₂—), 140.92 (2C—SO₂—). MS(M+H⁺): m/e 592.8907 (100%), 590.8933 (49%), 594.8884 (56%); exact massfor C₂₄H₁₇O₄Br₂S₂, 592.8909 (100%), 590.8930 (51.4%), 594.8889 (48.6).

Example 3 2,2′-Bis-benzenesulfonyl-4,4′-dibromobiphenyl-alternateprocedure

Inside a glove box, a 125 mL round-bottom flask equipped with a stirringbar, reflux condenser, and gas inlet was charged with4,4′-dibromobiphenyl-2,2′-disulfonyl dichloride (10.18 g, 20 mmoles) andaluminum chloride (5.87 g, 44 mmoles). Benzene (14 mL) and anhydrousnitromethane (40 mL) were added and the mixture stirred until dissolved.The solution was heated to 100° C. for about 8 hours. The solution wascooled to room temperature and poured onto 200 g ice mixed with 100 mLhydrochloric acid. The mixture was extracted several times withdichloromethane. The organic extracts were washed twice with water,dried with sodium carbonate, filtered, and evaporated to give 11.75 g(99%). The mixture was purified by column chromatography using silicagel and dichloromethane (R_(f) 0.32) to give 8.73 g (74% yield) of2,2′-bis-benzenesulfonyl-4,4′-dibromobiphenyl.

The reaction was repeated on a larger scale to give 24.37 g (87% yield)and purified by chromatography to give 17.2 g (61% yield). The combinedproducts were recrystallized from toluene after treating withdecolorizing carbon to give 23.02 g (89% mass balance) of2,2′-bis-benzenesulfonyl-4,4′-dibromobiphenyl.

Example 4

Inside the glove box, a 125 mL round-bottom flask equipped with a largestirring bar and a septum was charged withbis(1,5-cyclooctadiene)nickel(0) (2.09 g, 7.6 mmoles), cyclooctadiene(0.82 g, 7.6 mmoles), 2,2′-bipyridine (1.19 g, 7.6 mmoles), and DMAc (15mL). The flask was heated to 70° C. under nitrogen for 30 minutes togive a dark violet-colored solution. Inside the glove box, a 50 mLround-bottom flask equipped with a septum was charged with2,2′-bis-benzenesulfonyl-4,4′-dibromobiphenyl (2.05 g, 3.46 mmoles), andDMAc (15 mL). This flask was heated to 70° C. to dissolve the monomerand the solution was added by cannula to the reaction flask undernitrogen. The solution began to gel during addition and was completelygelled by the end. The temperature was increased to 100° C. and heldthere overnight.

The reaction mixture was poured into concentrated hydrochloric acid toprecipitate the polymer and the mixture was chopped in a blender todisperse the polymer into particles. The polymer was collected by vacuumfiltration using water to wash the polymer. The polymer was washed withconcentrated hydrochloric acid followed by water. The damp polymer waswashed with cyclohexane followed by methanol and dried in a vacuum ovenat 70° C. under nitrogen purge to give 1.32 g (88% yield) ofpoly[(2,2′-bis-benzenesulfonyl-4,4′-biphenylene)]. The polymer showedlow solubility in DMSO and DMAc. A broad ¹H NMR spectrum was obtained inDMSO-d₆ at 100° C.: 7.25, 7.59, 7.70, 7.73, 8.08, 8.38. The molecularweight distribution was measured by gel permeation chromatography inDMAc: M_(n) 15,300, M_(w) 202,000, M_(z) 1,200,000; [η] 4.49.Thermo-gravimetric analysis (10° C./min scan rate) showed an onset ofdecomposition at 435° C. under nitrogen. Differential scanningcalorimetry showed a glass transition temperature of 225° C.

Example 5

Inside the glove box, a 300 mL round-bottom flask equipped with a largestirring bar and a septum was charged with bis(1,5-cyclooctadiene)nickel(0) (11.11 g, 40.4 mmoles), cyclooctadiene (4.37 g, 40.4 mmoles),2,2′-bipyridine (6.31 g, 40.4 mmoles), and DMAc (120 mL). The flask washeated to 70° C. under nitrogen for 30 minutes to give a darkviolet-colored solution. Inside the glove box, a 100 mL round-bottomflask equipped with a septum was charged with2,2′-bis-benzenesulfonyl-4,4′-dibromobiphenyl (11.85 g, 20 mmoles), andDMAc (80 mL). This solution was quickly added by cannula to the reactionflask under nitrogen. The solution began to quickly increase inviscosity after the addition so the temperature was increased to 100° C.and held there for 1 hour.

The warm reaction mixture was poured into concentrated hydrochloric acid(250 mL) to precipitate the polymer and the mixture was chopped in ablender to disperse the polymer into particles. The polymer wascollected by vacuum filtration using water to wash the polymer. Thepolymer was washed with concentrated hydrochloric acid followed bywater. The damp polymer was washed with hexane followed by methanol anddried in a vacuum oven at 70° C. under nitrogen purge to give 8.35 g(97% yield) of poly[(2,2′-bis-benzenesulfonyl-4,4′-biphenylene)]. Thepolymer showed low solubility in DMSO and DMAc. A broad ¹H NMR spectrumwas obtained in DMSO-d₆ at 120° C.: 7.29, 7.63, 7.73, 7.74, 8.10, 8.41.The molecular weight distribution was measured by gel permeationchromatography in DMAc: M_(n) 19,400, M_(w) 83,800, M_(z) 244,000;[η]-4.32. Thermo-gravimetric analysis (10° C./min scan rate) showed anonset of decomposition at 400° C. under air. Differential scanningcalorimetry showed a glass transition temperature of 225° C.

Comparative Example 1

Inside the glove box, a 300 mL round-bottom flask equipped with a largestirring bar and a septum was charged withbis(1,5-cyclooctadiene)nickel(0) (11.11 g, 40.4 mmoles), cyclooctadiene(4.37 g, 40.4 mmoles), 2,2′-bipyridine (6.31 g, 40.4 mmoles), and DMAc(120 mL). The flask was heated to 70° C. under nitrogen for 30 minutesto give a dark violet-colored solution. Inside the glove box, a 100 mLround-bottom flask equipped with a septum was charged with2-benzenesulfonyl-1,4-dibromobenzene (7.52 g, 20 mmoles) and DMAc (80mL). This solution was quickly added by cannula to the reaction flaskunder nitrogen. The solution was stirred at 70° C. for 4 hours, but didnot develop any viscosity.

The cooled reaction mixture was poured into concentrated hydrochloricacid to precipitate the polymer and the mixture was chopped in a blenderto disperse the polymer into particles. The polymer was collected byvacuum filtration using water to wash the polymer. The polymer waswashed with concentrated hydrochloric acid followed by water then twicewith methanol. The damp polymer was dried in a vacuum oven at 70° C.under nitrogen purge to give 2.63 g (93% yield). The material showedsolubility in DMSO and DMAc. A complex ¹H NMR spectrum was obtained inDMSO-d₆ with major peaks at 6.7-8.9. The molecular weight distributionwas measured by gel permeation chromatography in DMAc: M_(n) 750, M_(w)3000, M_(w) 7,800; [η] 0.09. The material was too low in molecularweight to be considered the desired polymer,poly(benzenesulfonyl-1,4-phenylene).

Example 6

Inside the glove box, a 125 mL round-bottom flask equipped with a largestirring bar and a septum was charged withbis(1,5-cyclooctadiene)nickel(0) (2.78 g, 10.1 mmoles), cyclooctadiene(1.09 g, 10.1 mmoles), 2,2′-bipyridine (1.58 g, 10.1 mmoles), and DMAc(25 mL). The flask was heated to 70° C. under nitrogen for 30 minutes togive a dark violet-colored solution. Inside the glove box, a 50 mLround-bottom flask equipped with a septum was charged with2,2′-bis-benzenesulfonyl-4,4′-dibromobiphenyl (2.81 g, 4.75 mmoles),2-benzenesulfonyl-1,4-dibromobenzene (0.094 g, 0.25 mmoles) and DMAc (25mL). This solution was quickly added by cannula to the reaction flaskunder nitrogen. The solution began to thicken, but did not gel, so itwas stirred at 70° C. for 6 hours.

The cooled reaction mixture was poured into concentrated hydrochloricacid to precipitate the polymer and the mixture was chopped in a blenderto disperse the polymer into particles. The polymer was collected byvacuum filtration using methanol to wash the polymer. The polymer waswashed several times with concentrated hydrochloric acid followed bymethanol. The damp polymer was dried in a vacuum oven at 80° C. undernitrogen purge to give 2.17 g (100% yield) of the 95:5 copolymer,poly[(2,2′-bis-benzenesulfonyl-4,4′-biphenylene)-co-(benzenesulfonyl-1,4-phenylene)].The polymer showed low solubility in DMSO and DMAc. A broad ¹H NMRspectrum was obtained in DMSO-d₆ at 100° C.: 7.25, 7.60, 7.70, 7.71,8.07, 8.37. Thermo-gravimetric analysis (10° C./min scan rate) showed anonset of decomposition at 400° C. under air. Differential scanningcalorimetry showed a glass transition temperature of 224° C. This showsthat 5 mole percent comonomer had a negligible effect on the glasstransition temperature when compared to the homopolymers of Examples 4and 5.

Example 7

Inside the glove box, a 125 mL round-bottom flask equipped with a largestirring bar and a septum was charged withbis(1,5-cyclooctadiene)nickel(0) (2.78 g, 10.1 mmoles), cyclooctadiene(1.09 g, 10.1 mmoles), 2,2′-bipyridine (1.58 g, 10.1 mmoles), and DMAc(25 mL). The flask was heated to 70° C. under nitrogen for 30 minutes togive a dark violet-colored solution. Inside the glove box, a 50 mLround-bottom flask equipped with a septum was charged with2,2′-bis-benzenesulfonyl-4,4′-dibromobiphenyl (2.67 g, 4.5 mmoles),2-benzenesulfonyl-1,4-dibromobenzene (0.188 g, 0.50 mmoles) and DMAc (25mL). This solution was quickly added by cannula to the reaction flaskunder nitrogen. The solution began to thicken, but did not gel, so itwas stirred at 70° C. for 6 hours.

The cooled reaction mixture was poured into concentrated hydrochloricacid to precipitate the polymer and the mixture was chopped in a blenderto disperse the polymer into particles. The polymer was collected byvacuum filtration using methanol to wash the polymer. The polymer waswashed twice with concentrated hydrochloric acid followed by methanol.The damp polymer was dried in a vacuum oven at 80° C. under nitrogenpurge to give 2.05 g (100% yield) of the 90:10 copolymer,poly[(2,2′-bis-benzenesulfonyl-4,4′-biphenylene)-co-(benzenesulfonyl-1,4-phenylene)].A broad ¹H NMR spectrum was obtained in DMSO-d₆ at 100° C. with majorpeaks at 7.27, 7.62, 7.71, 7.73, 8.09, and 8.39, and minor peaks at6.96, 7.50, 7.95, 8.47, and 8.65. The molecular weight distribution wasmeasured by gel permeation chromatography in DMAc: M_(n) 9,820, M_(w)41,200, M_(z) 92,500; [η] 2.02. Thermo-gravimetric analysis (10° C./minscan rate) showed an onset of decomposition at 400° C. under air.Differential scanning calorimetry showed a glass transition temperatureof 223° C. This shows that 10 mole percent comonomer had a negligibleeffect on the glass transition temperature when compared to thehomopolymers of Examples 4 and 5.

The copolymer (0.5 g) was dissolved in DMAc at 160° C. to give 5.0weight % solution. The cooled solution was filtered using a glassmicrofiber syringe filter and poured into a glass film-casting dish,which was placed on a leveled drying stage in a nitrogen-purged dryingchamber. The dried film became slightly hazy and lifted free of the dishon its own. The film was further dried at 150° C. in a vacuum oven undernitrogen purge. The film was strong in tension, but was brittle as itbroke into pieces when folded over and creased.

The copolymer (0.5 g) was dissolved in 1,1,2,2-tetrachloroethane at roomtemperature to give 3.2 weight % solution. The solution was filteredusing a glass microfiber syringe filter and poured into a glassfilm-casting dish, which was placed on a leveled drying stage in anitrogen-purged drying chamber. The film was further dried at 80° C. ina vacuum oven under nitrogen purge. The film had become opaque and wasfloated free of the dish in water after scoring the edge. The film wasnot strong in tension and was brittle such that film could not even befolded over.

2-Benzenesulfonyl-1,4-dichlorobenzene

A modification of the published procedures of Hagberg, Olson, andSheares in Macromolecules, 2004, 37, 4748 was used. A 200 mLround-bottom flask equipped with a reflux condenser, stirring bar, andgas inlet was charged with 2,5-dichlorobenzenesulfonyl chloride (12.28g, 50 mmoles), benzene (13.4 mL, 150 mmoles), and anhydrous nitromethane(50 mL). Aluminum chloride (7.33 g, 55 mmoles) was added and the mixturestirred until dissolved under nitrogen. The solution was heated to 100°C. overnight. The solution was cooled to room temperature and pouredinto 100 g water mixed with 25 mL hydrochloric acid. The mixture wasextracted several times with dichloromethane. The organic extracts weredried with sodium sulfate, filtered, and evaporated, then the solidswere dried in a vacuum oven to give 14.38 g (100% crude yield). Thesolids were recrystallized from ethanol after treating with decolorizingcarbon to give about 14 g in two crops. The solids were recrystallizedfrom ethanol to give 12.24 g (85% yield) of2-benzenesulfonyl-1,4-dichlorobenzene. ¹H NMR (DMSO-d₆): 7.65 (ddd, 8.4,7.5, 1.7 Hz, 2H), 7.67 (d, 8.6 Hz, 1H), 7.76 (tt, 7.5, 1.2 Hz, 1H), 7.83(dd, 8.6, 2.6 Hz, 1H), 7.98 (ddd, 8.4, 1.7, 1.2 Hz, 2H), 8.27 (d, 2.6Hz, 1H).

4,4′-Dichlorobiphenyl-2,2′-disulfonic acid, sodium salt

A modification of the published procedures of Courtot and Lin in Bull.Soc. Chim. Fr. 1931, 49, 1047 was used. A 500 mL round-bottom flaskequipped with an addition funnel and stirring bar was charged withbenzidine-2,2′-disulfonic acid, 70% technical grade (34.4 g, 0.1 moles),ice (50 g), and hydrochloric acid (65 mL). The mixture was chilled to 0°C. in an ice bath. A solution of sodium nitrite (15 g, 0.22 moles)dissolved in water (50 mL) was added dropwise during which the diazoniumsalt precipitated from the resulting solution. The addition was stoppedwhen gas evolution was observed and the slurry was kept cold. A 1 Lround-bottom flask equipped with a stirring bar was charged withcopper(I) chloride (25 g, 0.25 moles) and hydrochloric acid (85 mL) togive a dark green solution then chilled to 0° C. in an ice bath. Thecold diazonium salt slurry was added slowly to the solution to giveimmediate gas evolution. The solution was stirred until it warmed toroom temperature and evaporated to remove excess hydrochloric acid. Thesolids were dissolved in water, treated with sodium carbonate to give pH7, which precipitate residual copper salts, filtered and evaporated togive a tan solid. The solids were recrystallized twice from ethanolafter treating with decolorizing carbon and dried under vacuum at 80° C.to give 9.0 g (21 yield) of 4,4′-dichlorobiphenyl-2,2′-disulfonic acid,sodium salt. ¹H NMR (DMSO-d₆): 7.19 (d, 8.3 Hz, 2H), 7.42 (dd, 8.3 and2.1 Hz, 2H), 7.96 (d, 2.1 Hz, 2H).

Example 8 4,4′-Dichlorobiphenyl-2,2′-disulfonic acid, sodium salt

Inside a glove box, a 300 mL round-bottom flask equipped with a refluxcondenser, stirring bar, and gas inlet was charged with anhydrous2,5-dichlorobenzenesulfonic acid, sodium salt (24.9 g, 0.1 moles),activated copper bronze (12.7 g, 0.2 moles), and DMAc (100 mL). Themixture was heated to 150° C. overnight under nitrogen. The mixture waspoured into water (1 L) and the solid removed by vacuum filtration. Thefiltrate was treated with sufficient sodium carbonate to precipitateresidual copper salts, which were removed by vacuum filtration. Thesolution was evaporated and the residue dried at 150° C. under vacuum.The solids (29.75 g) were dissolved in a mixture of ethanol and water,acidified with acetic acid, filtered, and concentrated to give an oil.The oil was dissolved in ethanol (100 mL) and allowed to set overnightto give a copious white solid, which was collected by vacuum filtrationand washed twice with ethanol. The solids were recrystallized twice fromethanol to give 10.05 g (47% yield) of4,4′-dichlorobiphenyl-2,2′-disulfonic acid, sodium salt. ¹H NMR(DMSO-d₆): 7.30 (d, 8.2 Hz, 2H), 7.34 (dd, 8.2, 2.3 Hz, 2H), 7.82 (d,2.2 Hz, 2H).

4,4′-Dichlorobiphenyl-2,2′-disulfonyl dichloride

A modification of the published procedures of Courtot and Lin in Bull.Soc. Chim. Fr. 1931, 49, 1047 was used. Inside a glove box, a 100 mLround-bottom flask equipped with a reflux condenser, stirring bar, andgas inlet was charged with 4,4′-dichlorobiphenyl-2,2′-disulfonic acid,sodium salt (18.8 g, 44 mmoles), phosphorus pentachloride (21 g, 100mmoles), and phosphorus oxychloride (42 mL). The mixture was heated to amild reflux (130° C.) for 6 hours under nitrogen. The mixture was pouredinto water (500 kg) and stirred about 45 minutes until the solids werefinely divided. The solids were collected by vacuum filtration, washedwell with water, and air dried on the filter then dried under vacuum at60° C. to give 17.13 g (93% crude yield). The solids were recrystallizedfrom toluene, collected by vacuum filtration, and dried under vacuum at80° C. A second crop was obtained by concentrating the filtrate anddiluting with hexane. The combined yield was 15.41 g (83%) of4,4′-dichlorobiphenyl-2,2′-disulfonyl dichloride. ¹H NMR (CDCl₃): 7.46(d, 8.2 Hz, 2H), 7.77 (dd, 8.2, 2.2 Hz, 2H), 8.24 (d, 2.2 Hz, 2H).

Example 9

Inside a glove box, a 125 mL round-bottom flask equipped with a stirringbar, reflux condenser, and gas inlet was charged with4,4′-dichlorobiphenyl-2,2′-disulfonyl dichloride (15.4 g, 36.7 mmoles),benzene (25 mL, 280 mmoles), and anhydrous nitromethane (75 mL).Aluminum chloride (11 g, 81 mmoles) was added and the mixture stirreduntil dissolved under nitrogen. The solution was heated to 100° C. for 8hours. The solution was cooled to room temperature and poured onto 200 gice mixed with 100 mL hydrochloric acid. The mixture was extractedseveral times with dichloromethane. The organic extracts were washedwith water, dried with sodium carbonate, filtered to give a darksolution. The solution was treated with decolorizing carbon and heatedto a reflux, then filtered through filter aid, evaporated, and thesolids dried at 150° C. in a vacuum oven for 8 hr to give 0.18.02 g (97%crude yield). The mixture was purified by column chromatography usingsilica gel and dichloromethane (R_(f) 0.28) to give 14.3 g (77% yield)of 2,2′-bis-benzenesulfonyl-4,4′-dichlorobiphenyl. The solids wererecrystallized from xylenes to give 13.08 g (71%). ¹H NMR (DMSO-d₆):6.96 (d, 8.2 Hz, 2H), 7.55 (bs, 4H), 7.56 (m, 8.1 Hz, 4H), 7.69 (m, 2H),7.74 (dd, 8.2, 2.2 Hz, 2H), 8.13 (d, 2.2 Hz, 2H). ¹³C NMR (CDCl₃):128.42 (4CH), 129.14 (4CH), 129.58 (2CH), 132.21 (2CH), 133.84 (2CH),134.13 (2CH), 134.68 (2C), 135.61 (2C), 140.42 (2C), 141.42 (2C). MS(M+H⁺): m/e 502.99 (100%), 504.99 (75%), exact mass for O₂₄H₁₇O₄Cl₂S₂,502.99 (100%), 504.99 (72.9%).

Example 10

Inside the glove box, a 50 mL round-bottom flask equipped with a largestirring bar and a septum was charged withbis(1,5-cyclooctadiene)nickel(0) (0.578 g, 2.1 mmoles), cyclooctadiene(0.227 g, 2.1 mmoles), 2,2′-bipyridine (0.328 g, 2.1 mmoles), and DMAc(5 mL). The flask was heated to 70° C. under nitrogen for 30 minutes togive a dark violet-colored solution. Inside the glove box, a 25 mLround-bottom flask equipped with a septum was charged with2,2′-bis-benzenesulfonyl-4,4′-dichlorobiphenyl (0.453 g, 0.9 mmoles),2-benzenesulfonyl-1,4-dichlorobenzene (0.029 g, 0.1 mmoles), and DMAc (5mL). This flask was heated to 70° C. to dissolve the monomers and thesolution was added by cannula to the reaction flask under nitrogen. Theviscosity of the solution increased slowly over the course of an hour asthe color faded to black.

After reacting overnight at 70° C., the reaction mixture was dilutedwith DMAc (20 mL), poured into concentrated hydrochloric acid toprecipitate the polymer, and rinsed from the flask with methanol andconcentrated hydrochloric acid. The mixture was chopped in a blender todisperse the polymer into particles. The polymer was collected by vacuumfiltration and rinsed from the blender jar with methanol, then washed onthe filter three times with a mixture of methanol and concentratedhydrochloric acid. The polymer was then washed alternatively with waterand methanol several times, and dried in a vacuum oven at 80° C. undernitrogen purge to give 0.41 g (100% yield) of the 90:10 copolymer,poly[(2,2′-bis-benzenesulfonyl-4,4′-biphenylene)-co-(benzenesulfonyl-1,4-phenylene)].The molecular weight distribution was measured by gel permeationchromatography in DMAc: M_(n) 60,100, M_(w) 331,000, M_(z) 1,600,000;[η] 9.12. Thermo-gravimetric analysis (10° C./min scan rate) showed anonset of decomposition at 400° C. under air. Differential scanningcalorimetry showed a glass transition temperature of 227° C. This showsthat 10 mole percent comonomer had no effect on the glass transitiontemperature when compared to the homopolymers of Examples 4 and 5, andwas in fact higher presumably due to the improved reactivity of thechlorine groups, which also led to higher molecular weights than thecopolymers of Examples 6 and 7.

The copolymer (0.1 g) was dissolved in 1,1,2,2-tetrachloroethane to give1.1 weight % solution. The solution was poured into a polymethylpentenePetri dish and placed on a leveled drying stage in a nitrogen-purgeddrying chamber. The dried film lifted free of the dish on its own. Thefilm was further dried at 60° C. in a vacuum oven under nitrogen purge.The film was strong, flexible, tough, and creasable.

Dynamic Mechanical Analysis of the film showed a high storage modulus of4112 MPa at 25° C. and good retention at elevated temperatures with avalue of 1396 MPa at 200° C. and about 1000 MPa at 220° C. The tan deltaplot confirmed the high Tg with a peak at 240° C. Compared topoly(2,5-benzophenone) with reported Tg of 149 to 217° C. (Wang andQuirk, Macromolecules 1995, 28 (10), p. 3495), the copolymer film showeda higher Tg and much better retention of storage modulus at temperaturesbetween 140 and 220° C.

1. A polymer comprising repeating units of Formula (I):

where T is a bulky aromatic group.
 2. The polymer of claim 1 that has anumber average molecular weight of at least about 5,000.
 3. The polymerof claim 1 wherein T is phenyl.
 4. The polymer of claim 1 furthercomprising repeating units of Formula (II):

where T′ is a bulky aromatic group.
 5. The polymer of claim 4 that has anumber average molecular weight of at least about 5,000.
 6. The polymerof claim 4 wherein T′ is phenyl.
 7. A compound of Formula (IA):

where T is a bulky aromatic group and X is Br or Cl.
 8. The compound ofclaim 7 where T is phenyl
 9. The compound of claim 7 where is Cl.
 10. Aprocess for preparing a polymer comprising polymerizing a monomer ofFormula (IA)

wherein T is a bulky aromatic group and X is independently Br or Cl. 11.The process of claim 10 where T is phenyl
 12. The process of claim 10where X is Cl.
 13. The process of claim 10 wherein the polymer has anumber average molecular weight of at least about 5,000.
 14. The processof claim 10 wherein the process comprises polymerizing a monomer ofFormula (IA) and a monomer of Formula (IIA)

wherein T′ is a bulky aromatic group and X′ is independently Br or Cl.15. The process of claim 10 where T and T′ are phenyl
 16. The process ofclaim 10 where X and X′ are Cl.
 17. The process of claim 14 wherein thepolymer has a number average molecular weight of at least about 5,000.18. The process of claim 10 wherein the polymerization is done in thepresence of a zerovalent transition metal and a neutral ligand in theform of a complex.
 19. The process of claim 18 wherein the zerovalenttransition metal is palladium or nickel.
 20. The process of claim 18wherein the zerovalent transition metal isbis(1,5-cyclooctadiene)nickel(0) and the neutral ligand is2,2′-bipyridine.